CN1935652A - Method for synthesizing ZSM-5 molecular sieve - Google Patents
Method for synthesizing ZSM-5 molecular sieve Download PDFInfo
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- CN1935652A CN1935652A CN 200610117265 CN200610117265A CN1935652A CN 1935652 A CN1935652 A CN 1935652A CN 200610117265 CN200610117265 CN 200610117265 CN 200610117265 A CN200610117265 A CN 200610117265A CN 1935652 A CN1935652 A CN 1935652A
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Abstract
The invention is a ZSM-5 molecular sieve synthesizing method, belonging to inorganic chemical synthesis technical field. And it prepares the ZSM-5 molecular sieve by preparing guiding agent and reacting mixed solution, hydrothermal crystallization, and routine filtering, washing, drying and baking, where the guiding agent uses tetrapropyl ammonium bromide or tetrapropyl ammonium hydroxide as the first organic alkali template and the reacting mixed solution uses annular molecular amine- hexamethylene imine or piperidine or their mixture as the second organic alkali template; and it has advantages of omitting ion exchange procedure, short process, low producing cost, not discharging ammonium- and nitrogen- containing waste water, not polluting environment, etc.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-5 molecular sieve, belong to inorganic chemical synthesis technical field.
Background technology
The ZSM-5 molecular sieve be by U.S. Mobil company in 1972 synthetic (US3,702,886) first.Because of it has the attention that special pore passage structure and catalytic performance, good thermostability and hydrothermal stability are subjected to domestic and international petrochemical complex circle, very important industrial chemical processes such as catalytic cracking, aromizing, alkylation, disproportionation have been widely used in.In general, the method for synthetic ZSM-5 molecular sieve is divided into use organic bases template has amine method non-amine method synthetic and that do not use organic bases to do template to synthesize.But adopted mineral alkali (as sodium hydroxide) in above two kinds of synthetic systems, its effect is mainly, the one, and as mineralizer, formation is suitable for required presoma of molecular sieve crystallization and alkaline environment, and the 2nd, alkalimetal ion is (as Na
+) in the molecular sieve crystallization process, play the effect of balance framework of molecular sieve negative charge.Synthetic to obtain molecular sieve be sodium type ZSM-5 molecular sieve, i.e. NaZSM-5 by above-mentioned system.Because Na among the NaZSM-5
+Balance the framework of molecular sieve negative charge, thereby molecular sieve shows electric neutrality, lacks the acid catalysis active centre.Therefore, in the last handling process of ZSM-5 molecular sieve, need carry out ion-exchange to NaZSM-5, make it to become ammonium type ZSM-5, i.e. NH with inorganic ammonium salt
4ZSM-5 deviates from ammonia through roasting again, obtains Hydrogen ZSM-5, i.e. HZSM-5.Widespread use at present be HZSM-5, abbreviate ZSM-5 as.
The shortcoming of at present synthetic ZSM-5 molecular sieve method is that synthesis technique all contains the operation that useful inorganic ammonium salt carries out ion-exchange to NaZSM-5, as US 3,702,886, CN1417116A, CN20041048353.5, have to contain the ammonium nitrogen wastewater discharging in a large number, serious to environmental influence.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of ZSM-5 molecular sieve, this method need be through the operation that adopts inorganic ammonium salt NaZSM-5 to be carried out ion-exchange, efficiently solve environmental pollution problems, shortened technical process simultaneously, help suitability for industrialized production.
The present invention achieves the above object by the following technical solutions:
By synthesizing of directed agents solution, the preparation of reaction mixture, hydrothermal crystallizing, again through filtration, washing, drying, the roasting of routine, make the ZSM-5 molecular sieve, directed agents solution is made the first organic bases template with 4-propyl bromide or TPAOH, and reaction mixture is made the second organic bases template with ring molecule amine-hexamethylene imine or piperidines or both mixtures.
Now describe technical scheme of the present invention in detail.
A kind of synthetic method of ZSM-5 molecular sieve is characterized in that, operation steps:
Synthesizing of the first step directed agents solution
SiO in the first silicon source in molar ratio
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2O is 1: (0.05～0.2): (0～0.1): (5～90), the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get the directed agents solution of clear, the first silicon source is tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters, the first aluminium source is Tai-Ace S 150, aluminum nitrate or aluminum chloride, and the first organic bases template is 4-propyl bromide or TPAOH;
The preparation of the second step reaction mixture
SiO in the second silicon source in molar ratio
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2O is 1: (0.1～4): (0～0.2): (5～90), and preparating mixture solution mixes the second organic bases template and water earlier, stir and add the second silicon source and aluminium source down, stir, add the directed agents solution that the first step makes again, the add-on of directed agents solution is SiO in the silicon source
20.1%～20% of weight, get reaction mixture, the second silicon source is tetraethyl orthosilicate, silicic acid orthocarbonate, silicic acid four butyl esters, silica gel or silicon sol, the second aluminium source is Tai-Ace S 150, aluminum nitrate or aluminum chloride, and the second organic bases template is the mixture of ring molecule amine-hexamethylene imine, piperidines or hexamethylene imine and piperidines;
The 3rd step hydrothermal crystallizing
Second reaction mixture that make of step is transferred to carries out hydrothermal crystallizing in the autoclave, the temperature and time of hydrothermal crystallizing is respectively 130～200 ℃ and 1～6 day, the good reaction mixture of hydrothermal crystallizing after the filtration of routine, washing, drying, roasting product, the ZSM-5 molecular sieve.
Of the present invention being further characterized in that, in the first step, the SiO in the first silicon source
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.1～0.15): (0～0.1): (10～40), the first silicon source is a tetraethyl orthosilicate, and the first aluminium source is a Tai-Ace S 150, and the first organic bases template is a TPAOH.
Of the present invention being further characterized in that, in second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.5～2): (0～0.1): (10～50), the add-on of directed agents solution are SiO in the second silicon source
21%～10% of weight.
Of the present invention being further characterized in that, in the 3rd step, the optimal value of the temperature and time of hydrothermal crystallizing is respectively 160～180 ℃ and 1～3 day.
Of the present invention being further characterized in that, in the first step, the SiO in the first silicon source
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.1～0.15): (0～0.1): (10～40), the first silicon source is a tetraethyl orthosilicate, and the first aluminium source is a Tai-Ace S 150, and the first organic bases template is a TPAOH; In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.5～2): (0～0.1): (10～50), the add-on of directed agents solution are SiO in the second silicon source
2Weight 1%～10%; In the 3rd step, the optimal value of the temperature and time of hydrothermal crystallizing is respectively 160～180 ℃ and 1～3 day.
Compared with prior art, the technology of the present invention has following remarkable advantage:
1, synthetic ZSM-5 molecular sieve under the system that does not contain mineral alkali has saved ion-exchange process, and technological process is short, and production cost is low.
2, whole technological process does not contain the ammonium nitrogen wastewater discharging because of not comprising ion-exchange process, has solved environmental pollution problems effectively.
3, introduce directed agents solution, good reproducibility.
Description of drawings
Fig. 1 is the XRD spectra before the embodiment 1 synthetic molecular sieve roasting.XRD determining is to carry out on German Bruker axs type X-ray diffractometer, adopts CuK α diffraction, sweep limit 2 θ=5～35 °.From XRD spectra as can be known, the position of diffraction peak in 2 θ=7.8 °, 8.8 °, 23.2 °, 23.8 °, 24.3 ° etc. strong diffraction peak appears, illustrate that embodiment 1 synthetic molecular sieve has typical ZSM-5 molecular sieve structure, i.e. the MFI structure.
Embodiment
All embodiment all operate by the operation steps of technique scheme.Each embodiment is only enumerated crucial technical data.
Embodiment 1
In the first step, the SiO in the first silicon source
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2The mol ratio of O is 1: 0.1: 0.04: 20, the first silicon sources are tetraethyl orthosilicate, and the first aluminium source is a Tai-Ace S 150, and the first organic bases template is a TPAOH; In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The mol ratio of O is 1: 1: 0.033: 12, and the add-on of directed agents solution is SiO in the second silicon source
23%, the second silicon source of weight is a silica gel, and the second aluminium source is a Tai-Ace S 150, and the second organic bases template is a hexamethylene imine; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 170 ℃ and 4 days.
The XRD spectra of the ZSM-5 molecular sieve of present embodiment as shown in Figure 1.
Embodiment 2
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, the SiO in the first silicon source
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2The mol ratio of O is 1: 0.2: 0.1: 80; In second step, the second organic bases template is the mixture of hexamethylene imine and piperidines, and the mol ratio of hexamethylene imine and piperidines is 5: 5.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 3
Implementation process except for the following differences, all the other are all with embodiment 1:
In second step, the second organic bases template is a piperidines, and the add-on of directed agents solution is SiO in the second silicon source
215% of weight.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 4
Implementation process except for the following differences, all the other are all with embodiment 1:
In second step, the second silicon source is a silicon sol, and the add-on of directed agents solution is SiO in the silicon source
28% of weight; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 150 ℃ of water and 5 days.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Implementation process except for the following differences, all the other are all with embodiment 1:
In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The mol ratio of O is 1: 0.6: 0.02: 12; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 160 ℃ and 4 days.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 6
Implementation process except for the following differences, all the other are all with embodiment 2:
In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The mol ratio of O is 1: 1.5: 0.02: 20; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 180 ℃ and 2 days.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 7
Implementation process except for the following differences, all the other are all with embodiment 1:
In second step, the second aluminium source is an aluminum nitrate, and the second organic bases template is the mixture of hexamethylene imine and piperidines, and the mol ratio of hexamethylene imine and piperidines is 8: 2; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 160 ℃ and 5 days.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 8
Implementation process except for the following differences, all the other are all with embodiment 2:
In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The mol ratio of O is 1: 1.5: 0.02: 10; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 180 ℃ and 2 days.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 9
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, the SiO in the first silicon source
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2The mol ratio of O is 1: 0.1: 0: 20; In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The mol ratio of O is 1: 1: 0: 10 preparating mixture solution; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 180 ℃ and 2 days.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Implementation process except for the following differences, all the other are all with embodiment 1:
In second step, the second organic bases template is the mixture of hexamethylene imine and piperidines, and the mol ratio of hexamethylene imine and piperidines is 5: 5.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 11
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, the first silicon source is silicic acid four butyl esters, and the first aluminium source is an aluminum nitrate, and the first organic bases template is a 4-propyl bromide; In second step, the second silicon source is a silica gel, and the second aluminium source is an aluminum chloride, and the second organic bases template is the mixture of hexamethylene imine and piperidines, and the mol ratio of hexamethylene imine and piperidines is 8: 2.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 12
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, the first silicon source is the silicic acid orthocarbonate; In second step, the second silicon source is a tetraethyl orthosilicate.
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar.
Embodiment 13
Implementation process except for the following differences, all the other are all with embodiment 1:
In the first step, the first aluminium source is an aluminum chloride; In second step, the second organic bases template is the mixture of hexamethylene imine and piperidines, and the mol ratio of hexamethylene imine and piperidines is 3: 7;
XRD spectra and Fig. 1 of the ZSM-5 molecular sieve of present embodiment are similar; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 175 ℃ and 5 days.
Embodiment 14
Implementation process except for the following differences, all the other are all with embodiment 2:
In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The mol ratio of O is 1: 3.5: 0.02: 80; In the 3rd step, the temperature and time of hydrothermal crystallizing is respectively 180 ℃ and 3 days.
Claims (5)
1, a kind of synthetic method of ZSM-5 molecular sieve is characterized in that, operation steps:
Synthesizing of the first step directed agents solution
SiO in the first silicon source in molar ratio
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2O is 1: (0.05～0.2): (0～0.1): (5～90), the preparation reaction mixture solution, be hydrolyzed into glue under the room temperature, get the directed agents solution of clear, the first silicon source is tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters, the first aluminium source is Tai-Ace S 150, aluminum nitrate or aluminum chloride, and the first organic bases template is 4-propyl bromide or TPAOH;
The preparation of the second step reaction mixture
SiO in the second silicon source in molar ratio
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2O is 1: (0.1～4): (0～0.2): (5～90), and preparating mixture solution mixes the second organic bases template and water earlier, stir and add the second silicon source and aluminium source down, stir, add the directed agents solution that the first step makes again, the add-on of directed agents solution is SiO in the silicon source
20.1%～20% of weight, get reaction mixture, the second silicon source is tetraethyl orthosilicate, silicic acid orthocarbonate, silicic acid four butyl esters, silica gel or silicon sol, the second aluminium source is Tai-Ace S 150, aluminum nitrate or aluminum chloride, and the second organic bases template is the mixture of hexamethylene imine, piperidines or hexamethylene imine and piperidines;
The 3rd step hydrothermal crystallizing
Second reaction mixture that make of step is transferred to carries out hydrothermal crystallizing in the autoclave, the temperature and time of hydrothermal crystallizing is respectively 130～200 ℃ and 1～6 day, the good reaction mixture of hydrothermal crystallizing after the filtration of routine, washing, drying, roasting product, the ZSM-5 molecular sieve.
2, the synthetic method of ZSM-5 molecular sieve according to claim 1 is characterized in that, in the first step, and the SiO in the first silicon source
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.1～0.15): (0～0.1): (10～40), the first silicon source is a tetraethyl orthosilicate, and the first aluminium source is a Tai-Ace S 150, and the first organic bases template is a TPAOH.
3, the synthetic method of ZSM-5 molecular sieve according to claim 1 is characterized in that, in second step, and the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.5～2): (0～0.1): (10～50), the add-on of directed agents solution are SiO in the second silicon source
21%～10% of weight.
4, the synthetic method of ZSM-5 molecular sieve according to claim 1 is characterized in that, in the 3rd step, the optimal value of the temperature and time of hydrothermal crystallizing is respectively 160～180 ℃ and 1～3 day.
5, the synthetic method of ZSM-5 molecular sieve according to claim 1 is characterized in that, in the first step, and the SiO in the first silicon source
2: the first organic bases template: the Al in the first aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.1～0.15): (0～0.1): (10～40), the first silicon source is a tetraethyl orthosilicate, and the first aluminium source is a Tai-Ace S 150, and the first organic bases template is a TPAOH; In second step, the SiO in the second silicon source
2: the second organic bases template: the Al in the second aluminium source
2O
3: H
2The optimal value of O mol ratio is 1: (0.5～2): (0～0.1): (10～50), the add-on of directed agents solution are SiO in the second silicon source
21%～10% of weight; In the 3rd step, the optimal value of the temperature and time of hydrothermal crystallizing is respectively 160～180 ℃ and 1～3 day.
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| CN102190317A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | ZSM-5 sieve material used for aromatic hydrocarbons alkylation reaction and preparation method thereof |
| CN102897793A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Sodium-free synthesis method for ZSM-5 molecular sieve |
| CN103304430A (en) * | 2013-07-05 | 2013-09-18 | 武汉科梦环境工程有限公司 | Process for recovering organic amine from catalyst production wastewater |
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| CN1032910C (en) * | 1993-09-20 | 1996-10-02 | 中国石油化工总公司 | Synthetizing BETA zeolite by guide agent method |
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| CN102190317B (en) * | 2010-03-03 | 2013-01-23 | 中国石油化工股份有限公司 | ZSM-5 sieve material used for aromatic hydrocarbons alkylation reaction and preparation method thereof |
| CN102897793A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Sodium-free synthesis method for ZSM-5 molecular sieve |
| CN102897793B (en) * | 2011-07-29 | 2014-12-03 | 中国石油化工股份有限公司 | Sodium-free synthesis method for ZSM-5 molecular sieve |
| CN104108725A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for preparing ZSM-35 molecular sieve |
| CN104108725B (en) * | 2013-04-16 | 2016-09-07 | 中国石油化工股份有限公司 | The method preparing ZSM-35 molecular sieve |
| CN103304430A (en) * | 2013-07-05 | 2013-09-18 | 武汉科梦环境工程有限公司 | Process for recovering organic amine from catalyst production wastewater |
| CN112774722A (en) * | 2019-11-11 | 2021-05-11 | 中国石油天然气股份有限公司 | Naphthenic aromatic selective ring-opening catalyst and preparation method thereof |
| CN112774722B (en) * | 2019-11-11 | 2023-08-22 | 中国石油天然气股份有限公司 | Naphthene arene selective ring-opening catalyst and preparation method thereof |
| CN114426455A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Benzene and ethylene alkylation reaction |
| CN114349021A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Preparation method of ZSM-5 zeolite molecular sieve with special morphology |
| CN116062769A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogen ZSM-5 molecular sieve and preparation method thereof, and xylene isomerization catalyst and preparation method thereof |
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